CN1510087A - Extraction of caramel pigment from waste liquid of molasses alcohol production - Google Patents
Extraction of caramel pigment from waste liquid of molasses alcohol production Download PDFInfo
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- CN1510087A CN1510087A CNA021281017A CN02128101A CN1510087A CN 1510087 A CN1510087 A CN 1510087A CN A021281017 A CNA021281017 A CN A021281017A CN 02128101 A CN02128101 A CN 02128101A CN 1510087 A CN1510087 A CN 1510087A
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- caramel colorant
- filtration membrane
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Abstract
A process for extracting the caramel pigment from the molasses alcohol sewage includes such steps as removing insoluble organic substances, ultrafiltering to obtain the liquid caramel pigment, and drying to obtain powdered one. Its advantages are high output rate (more than 90%), agreeable smell, and no environmental pollution.
Description
(1) technical field:
The present invention relates to the food dye field, specifically relate to from molasses alcohol waste liquid, extract the method for caramel colorant.
(2) background technology:
Caramel colorant claims dark reddish brown again, it is the liquid jelly of a kind of sorrel or chocolate, also can be dried to solid powdery, be a kind of in the food dye, be widely used in soy sauce, mature vinegar, candy, coffee, can, beverage, the painted of color wine, cake, tobacco, the cured pot-stewed fowl of burning, medical syrup etc. arranged.Food and Argriculture OrganizationFAO, the World Health Organization, European Union, U.S. food and FAD and China food industry associations all classify caramel colorant as natural food colour.On the consumption market, caramel colorant is the kind that has the call in the natural food colour, Japan is the country of natural food colour usage quantity maximum, annual consumption is more than 5000 ton, wherein caramel colorant just reaches 2000 tons, account for 40% of natural food colour total amount consumed, China produces natural food colour 1.8～20,000 ton per year, and wherein caramel colorant accounts for 80%.
The production of caramel colorant at present is raw material with sugar (maltose, glucose, sucrose, molasses) all, makes by caramelization or sugar-amine reaction under certain condition.We will utilize the manufacture method of these two kinds of reactions to be called non-ammonia process (caramelization) and ammonia process (sugar-amine reaction) usually.During non-ammonia process is produced, require strict controlling reaction time under higher temperature of reaction (about 200 ℃), reactant concn and pH value if the time has been grown, easily generate the material or the water-fast melanochrome of bitter.To add ammoniation in the ammonia process production, usually use ammonium chloride, ammonium sulfate, ammoniacal liquor or liquefied ammonia, temperature of reaction low (110～130 ℃), scorch time is short, the product strong coloring force, but introduced the byproduct 4-methylimidazole, it is a kind of convulsant, and the content in product must be less than the 200mg/kg caramel colorant.Because the existence of 4-methylimidazole makes the usage quantity of the caramel colorant that ammonia process is produced be restricted, and allow people's every day intake (ADI) to be defined as 0～100mg/kg, but not the caramel colorant product that ammonia process is produced does not then have this restriction.
Rolled up the 59th～61 page in 1998 the total the 15th at " fine chemistry industry " magazine, " the cane sugar factory alcohol residue extracts the research of food dye " disclosed, this method is extracted caramel colorant from the waste liquid (be alcohol residue, the present invention is referred to as molasses alcohol waste liquid) of producing the molasses regeneration of by-product after the sucrose and producing gained behind the alcohol.In molasses alcohol waste liquid, approximately there is 3～5% caramel colorant, utilize Hydrogen ion exchange resin with the caramel colorant enrichment, use the NaOH eluant solution then, collect the elutriant of PH≤7, reconcentration is to the underflow shape, be the caramel colorant liquid product, also the underflow drying can be made powder-like product, recovery rate is 1%.This method is the physics method, products obtained therefrom does not contain 4-methylimidazole, need not the strict control condition on the technology yet, and equipment is simple, work simplification is easy to operate, and be the useless wine with dregs that utilizes after molasses are produced alcohol, therefore, than directly producing caramel colorant with molasses, effect with comprehensive utilization, both produced alcohol, reclaimed caramel colorant again, solved the pollution of alcohol slops environment.But the yield of its caramel colorant is still lower, approximately can only receive in the alcohol residue contained caramel colorant 30%, and easily contain the phenols pigment in the pigment that reclaims, influence quality product, and, has more increased trade effluent owing to regeneration of resin and wash-out etc.
(3) summary of the invention
The purpose of this invention is to provide the method for from molasses alcohol waste liquid, extracting caramel colorant expeditiously, and be more conducive to reduce environmental pollution.
For achieving the above object, the present invention is raw material with the molasses alcohol waste liquid, removes earlier insoluble organism wherein, then with gained liquid through ultrafiltration membrance filter, trapped substance is caramel colorant.
Remove insoluble organic method centrifugation, sedimentation, filtration or micro-filtrate membrane filtration method are arranged.Wherein the most frequently used is centrifugation, because its efficient height need not add other material, good separating effect.In order to guarantee particularly to comprise the solid impurity of bringing in the raw material less in the liquid product in the finished product as far as possible, after the process centrifugation, also common filtration operation together can added, promptly use 300～1500 purpose screen filtrations once, not only convenient but also remove solid impurity trickle in the raw material more reliably.
The clear liquid that the above-mentioned processing of process obtains, what contain nearly all is the ion of water miscible pigment, metal ion, organic acid or mineral acid and a large amount of water, different according to the molecular weight of these compositions and physical and chemical performance, membrane filtration is a kind of the most effective the simplest separation method that can not introduce any tramp material again.The ultra-filtration membrane that uses during ultrafiltration membrance filter of the present invention can be organic ultra-filtration membrane, also can be inorganic ultra-filtration membrane or composite hyperfiltration membrane.Ultra-filtration membrane can be charged, can be not charged yet because a little less than the caramel colorant electric polarity, other need remove composition in the liquid lotus positive electricity, and the bear electricity is also arranged, thus with non-charged membrane for well.
Organic ultra-filtration membrane is made by cellulose acetate, aromatic polyamides, polysulfonamides, polyethersulfone, polyacrylonitrile, polyethylene nitrile, polyvinyl alcohol, polyvinyl chloride or polyvinylidene difluoride (PVDF).Inorganic ultra-filtration membrane is made by sintered glass, silicon, silicon-dioxide, titanium dioxide, aluminum oxide, zirconium white or zeolite.Composite hyperfiltration membrane is organic ultra-filtration membrane of porous supporting body surface attachment one deck or the inorganic ultra-filtration membrane of making in organic materials or inorganic materials.The composite hyperfiltration membrane structure is strong, can bear higher pressure reduction, porous supporting body is easy to manufacture, cost is low, and the organic ultra-filtration membrane or the comparable unitary film of inorganic ultra-filtration membrane of surface attachment are thinner, thereby separation performance is better, required operting differential pressure is lower, price comparison is cheap, and in practical application, composite hyperfiltration membrane uses the most extensive.The ultrafiltration hole of the boring ratio surface film of porous supporting body is much bigger, and the liquid that is beneficial under surperficial membrane filtration passes through smoothly.Inorganic porous supporter has sintered ceramic, zirconium white, aluminum oxide, sintered glass etc., and organic porous supporting body has polysulfones, vinylidene etc.
The molecular weight cut-off of ultra-filtration membrane is related to the yield of separating effect and effective constituent, is an important indicator selecting ultra-filtration membrane for use.From the analytical results of material composition, take all factors into consideration separating effect and product yield, think that the molecular weight cut-off scope of ultra-filtration membrane should be 1000～300000.When molecular weight cut-off too little, then can be in product remaining a lot of small molecular weight impurity, if molecular weight cut-off is too big, a lot of effective constituents will be run off and will cause that yield reduces, in the actual production, be the best with 5000～30000.
Ultra-filtration membrane separates to be needed to increase certain pressure above film, or it is poor to make certain vacuum formation film pressure at both sides below film, and pressure difference big filter speed is big.But pressure difference proposes the requirement of withstand voltage height to device greatly, and design cost can raise.
Ultrafiltration membrance filter is not only relevant with the molecular weight cut-off of film, and relevant with the material of film.Select when suitable when mould material, can make required effective ingredient not have any loss and nearly 100% regain, impurity comprises that the phenols pigment in the molasses alcohol waste liquid all separates substantially with caramel colorant, thereby is a kind of extracting method of high yield.Utilize method of the present invention, the liquid caramel pigment product 80～300ml that can from the 1000ml stock liquid, receive qualifiedly, dry that the solid powder and granule shape caramel colorant produces 10～45g, yield reaches 1～4.5%, and caramel colorant contained in the raw material is recyclable more than 90%.
In the method for from molasses alcohol waste liquid, extracting caramel colorant of the present invention, take place without any chemical reaction, do not add any Chemical Composition yet, therefore, the caramel colorant product of the gained 4-methylimidazole that do not contain hazardous substance, remaining every index also meets the requirement (table 1 with the back describes in detail) of GB8817-2001 fully, and smell is pure, free from extraneous odour, product is the color developing basically identical under different PH conditions, high temperature resistant, solid phase prod favorable solubility, clear and bright, no muddy, the nothing precipitation of liquid product.
Table 1
The project standard-required detects knot
Really
Absorbancy E (0.1%, 1cm, 0.05～0.104～610nm) 0.6 0.258
Ammonia nitrogen (in NH3), %≤0.50 does not detect
4-methylimidazole %≤0.02 does not detect
Arsenic (in As) mg/ml≤1.0 do not detect
Plumbous (in Pb) mg/ml≤2.0 1.664
Operation of the present invention is more simpler than ion exchange resin concentration method, because it is without wash-out, and Just because of this, the present invention does not have regenerating resin and washes the processing wastewater that post brings, and more helps reducing environmental pollution.In actual production, the present invention only need read and see through liquid measure under feed liquor amount and the film, has just controlled the quality index of product and the output of product fully.Here, the process of membrane filtration in fact also is the spissated process of product (water can pass through film), for liquid product, reduce the energy consumption of concentrated or dry this procedure of knowing clearly on the technology, this improves yield to guaranteeing quality product, and it all is favourable reducing facility investment and saving energy spending.
(4) embodiment
Implementing the present invention does not need too big place, and required equipment is also very simple, just a bench centrifuge and a cover membrane filter appts.If pressure filtration then must make membrane filter appts can tolerate enough pressure, and increase a pressurizing device; If vacuum filtration then needs a cover vacuum decompression system in addition.The ultra-filtration membrane that the present invention uses belongs to the specification product on the market, can be by commercially available acquisition.
Embodiment one
With 1 liter of the waste liquid that produces behind the molasses fermented production alcohol, under the rotating speed of whizzer, separated 15 minutes at 4500r/min, take out clear liquid with 1500 purpose screen filtrations, filtrate injection film filter.Film is selected the non-charged composite hyperfiltration membrane of polyethersulfone for use, and molecular weight cut-off is 10000.0.2MPa filter, after film was collected 910ml liquid down, the liquid of holding back on the film was liquid caramel pigment (90ml).
Embodiment two
The liquid caramel pigment of embodiment one gained in 98 ℃ of vacuum-drying 8h, is ground and promptly gets powder shape caramel colorant 12g.
Embodiment three
According to the mode of embodiment one, just the molecular weight cut-off of ultra-filtration membrane being used instead is 3000, and pressurization 0.35MPa filters, and film is collected 700ml liquid down, and the liquid caramel pigment of holding back on film is 300ml.By embodiment two handle powder shape caramel colorant 45g.
Embodiment four
According to the mode of embodiment one, just ultra-filtration membrane is got molecular weight cut-off changes 250,000 into, and pressurization 0.1MPa filters, and after film was collected 800ml liquid down, the liquid caramel pigment of holding back on film was 200ml.Obtain powder shape caramel colorant 9g by embodiment two processing.
Embodiment five
According to the mode of embodiment one, just change ultra-filtration membrane into polyacrylonitrile non-charged composite hyperfiltration membrane, molecular weight cut-off is 50,000, and pressurization 0.25MPa filters, and after film was collected 750ml liquid down, the liquid caramel pigment of holding back on film was 250ml.Obtain powder shape caramel colorant 27g according to embodiment two processing.
Embodiment six
According to the mode of embodiment one, just change ultra-filtration membrane into the zeolite ultra-filtration membrane, molecular weight cut-off is 100,000, and pressurization 0.2MPa filters, and after film was collected 750ml liquid down, the liquid caramel pigment of holding back on film was 240ml.Obtain powder shape caramel colorant 14g according to embodiment two processing.
Embodiment seven
According to the mode of embodiment one, change ultra-filtration membrane into zirconium white-ceramic inorganic compounding tubular ultra-filtration membrane, molecular weight cut-off is 10,000, and pressurization 0.25MPa filters, and after film was collected 760ml liquid down, the liquid caramel pigment of holding back on film was 230ml.Obtain powder shape caramel colorant 40g according to embodiment two processing.
Embodiment eight
According to the mode of embodiment one, it is 30,000 that the molecular weight cut-off of ultra-filtration membrane is used instead, and after vacuum filtration, film were collected 750ml liquid down, the liquid caramel pigment of holding back on film was 240ml.Obtain powder shape caramel colorant 38g according to embodiment two processing.
Embodiment nine
According to the mode of embodiment one, change ultra-filtration membrane into cellulose acetate non-charged organic ultra-filtration membrane, the molecular weight cut-off of film is 1.5 ten thousand, after pressurization 0.2MPa, film collected 800ml liquid down, the liquid caramel pigment of holding back on film was 200ml.Obtain powder shape caramel colorant 20g according to embodiment two processing.
Claims (9)
1. from molasses alcohol waste liquid, extract the method for caramel colorant, contain following steps:
A) remove insoluble organism;
B) with A) gained is through ultrafiltration membrance filter, and trapped substance is caramel colorant;
C) with B) gained is through concentrating or be drying to obtain the caramel colorant product.
2. the method for extracting caramel colorant from molasses alcohol waste liquid according to claim 1, it is characterized in that removing insoluble organic method is centrifugation, sedimentation, filtration or microfiltration method.
3. the method for extracting caramel colorant from molasses alcohol waste liquid according to claim 1 is characterized in that ultra-filtration membrane is organic ultra-filtration membrane, inorganic ultra-filtration membrane or composite hyperfiltration membrane.
4. according to claim 1 or the 3 described methods of from molasses alcohol waste liquid, extracting caramel colorant, it is characterized in that ultra-filtration membrane can be charged or non-charged.
5. according to claim 1 or the 3 described methods of from molasses alcohol waste liquid, extracting caramel colorant, it is characterized in that organic ultra-filtration membrane made by cellulose acetate, aromatic polyamides, polysulfonamides, polyethersulfone, polyacrylonitrile, polyethylene nitrile, polyvinyl alcohol, polyvinyl chloride or polyvinylidene difluoride (PVDF).
6. according to claim 1 or the 3 described methods of from molasses alcohol waste liquid, extracting caramel colorant, it is characterized in that inorganic ultra-filtration membrane made by sintered glass, silicon, silicon-dioxide, titanium dioxide, aluminum oxide, zirconium white or zeolite.
7. according to claim 1 or the 3 described methods of from molasses alcohol waste liquid, extracting caramel colorant, it is characterized in that composite hyperfiltration membrane is organic ultra-filtration membrane of porous supporting body surface attachment one deck or the inorganic ultra-filtration membrane of making in organic materials or inorganic materials.
8. according to claim 1 or the 3 described methods of extracting caramel colorant from molasses alcohol waste liquid, the molecular weight cut-off that it is characterized in that ultra-filtration membrane is 1000～300000.
9. the method for extracting caramel colorant from molasses alcohol waste liquid according to claim 8, the molecular weight cut-off that it is characterized in that ultra-filtration membrane is 5000～30000.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021281017A CN1510087A (en) | 2002-12-24 | 2002-12-24 | Extraction of caramel pigment from waste liquid of molasses alcohol production |
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| Application Number | Priority Date | Filing Date | Title |
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| CNA021281017A CN1510087A (en) | 2002-12-24 | 2002-12-24 | Extraction of caramel pigment from waste liquid of molasses alcohol production |
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| CN1510087A true CN1510087A (en) | 2004-07-07 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864190A (en) * | 2010-06-13 | 2010-10-20 | 华南理工大学 | Method for preparing caramel colorant by using multistage membrane separation |
| CN102977629A (en) * | 2012-11-30 | 2013-03-20 | 广西崇左市湘桂糖业有限公司 | Method for preparing caramel pigment from molasses |
| CN104559305A (en) * | 2014-12-24 | 2015-04-29 | 华南理工大学 | Method for preparing caramel pigment from molasses yeast fermenting supernatant |
| CN108471769A (en) * | 2015-11-10 | 2018-08-31 | 科汉森天然色素有限责任公司 | Pigment derived from the caramel of brightness with raising |
| CN108928943A (en) * | 2018-07-09 | 2018-12-04 | 格翎（上海）环境科技有限公司 | A method of the alcohol effluent of processing molasses-spirit plant emissions |
| CN112791148A (en) * | 2020-12-27 | 2021-05-14 | 贵州瑞和制药有限公司 | Purification method for producing high-purity chuanshentong injection |
-
2002
- 2002-12-24 CN CNA021281017A patent/CN1510087A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864190A (en) * | 2010-06-13 | 2010-10-20 | 华南理工大学 | Method for preparing caramel colorant by using multistage membrane separation |
| CN101864190B (en) * | 2010-06-13 | 2012-10-31 | 华南理工大学 | Method for preparing caramel colorant by using multistage membrane separation |
| CN102977629A (en) * | 2012-11-30 | 2013-03-20 | 广西崇左市湘桂糖业有限公司 | Method for preparing caramel pigment from molasses |
| CN104559305A (en) * | 2014-12-24 | 2015-04-29 | 华南理工大学 | Method for preparing caramel pigment from molasses yeast fermenting supernatant |
| CN108471769A (en) * | 2015-11-10 | 2018-08-31 | 科汉森天然色素有限责任公司 | Pigment derived from the caramel of brightness with raising |
| CN108471769B (en) * | 2015-11-10 | 2022-02-11 | 科汉森天然色素有限责任公司 | Caramel-derived color with enhanced brightness |
| CN108928943A (en) * | 2018-07-09 | 2018-12-04 | 格翎（上海）环境科技有限公司 | A method of the alcohol effluent of processing molasses-spirit plant emissions |
| CN108928943B (en) * | 2018-07-09 | 2021-08-20 | 格翎（上海）环境科技有限公司 | Method for treating alcohol waste liquid discharged from molasses alcohol factory |
| CN112791148A (en) * | 2020-12-27 | 2021-05-14 | 贵州瑞和制药有限公司 | Purification method for producing high-purity chuanshentong injection |
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